Using Fourier self-deconvolution (FSD) to enhance spectral resolution of AOTF atomic emission spectrometer is described. Choosing the appropriate deconvolution parameters: full width at half maximum (FWHM) and breaking point, the FWHM of the simulated overlapping peaks could be decreased by a factor of 3.5, and the peak height by a factor of 5, but retaining the peak position. Practical samples of La and Ca-Al mixture were scanned by AOTF-ICP-AES respectively, the overlapping spectra of La 407.735 nm and La 408.672 nm as well as Ca 393.366 nm and Al 394.401 nm were well resolved into their respective lines after FSD; as to sample of Eu-Sr mixture and Sc-Sr mixture, after FSD treatment, the overlapping spectra of Eu 420.505 nm and Sr 421.552 nm as well as Sc 424.693 nm and Sr 421.552 nm at various concentration of Eu and Sc respectively were also well resolved into their respective lines. The slopes of their corresponding calibration curves were increased by a factor of 2 to 3.